EP0126830B1 - Procédé de transformation de sels difficilement solubles de colorants ou d'agents de blanchiment optiques anioniques en sels plus facilement solubles, par échange de cations - Google Patents

Procédé de transformation de sels difficilement solubles de colorants ou d'agents de blanchiment optiques anioniques en sels plus facilement solubles, par échange de cations Download PDF

Info

Publication number
EP0126830B1
EP0126830B1 EP83810251A EP83810251A EP0126830B1 EP 0126830 B1 EP0126830 B1 EP 0126830B1 EP 83810251 A EP83810251 A EP 83810251A EP 83810251 A EP83810251 A EP 83810251A EP 0126830 B1 EP0126830 B1 EP 0126830B1
Authority
EP
European Patent Office
Prior art keywords
solution
dye
dialysis
soluble salts
process according
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
EP83810251A
Other languages
German (de)
English (en)
Other versions
EP0126830A1 (fr
Inventor
Roger Dr. Lacroix
Hans-Rudolf Dr. Marfurt
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Novartis AG
Original Assignee
Ciba Geigy AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ciba Geigy AG filed Critical Ciba Geigy AG
Publication of EP0126830A1 publication Critical patent/EP0126830A1/fr
Application granted granted Critical
Publication of EP0126830B1 publication Critical patent/EP0126830B1/fr
Expired legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B69/00—Dyes not provided for by a single group of this subclass
    • C09B69/02—Dyestuff salts, e.g. salts of acid dyes with basic dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
    • C09B62/02—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group directly attached to a heterocyclic ring
    • C09B62/04—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group directly attached to a heterocyclic ring to a triazine ring
    • C09B62/08—Azo dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0096—Purification; Precipitation; Filtration
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
    • D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
    • D06L4/60—Optical bleaching or brightening
    • D06L4/664—Preparations of optical brighteners; Optical brighteners in aerosol form; Physical treatment of optical brighteners

Definitions

  • the invention relates to a process for converting poorly soluble salts of anionic dyes and optical brighteners into more soluble salts.
  • solubility of the salts of anionic dyes and optical brighteners in water or organic solvents not only depends on the constitution of the dye or brightener, but is also primarily dependent on the respective salt form, i.e. H. determined by the cation.
  • the sodium salts generally obtained in the synthesis are in many cases not readily water-soluble, but the same dyes or brighteners in the lithium salt form show a significantly higher water solubility (see, for example, DE-C-16 44 308).
  • dye or brightener salts with good water solubility are required, because this is the only way to keep the solvent content in the preparations as low as possible.
  • a high solubility of the dye or brightener is also advantageous in the production of solid preparations, since this enables gentle and energy-saving drying, since highly concentrated starting solutions can be used.
  • this process can only be used to carry out salting reactions, for example of dyes containing sulfo groups, in the presence of cations whose molecular weight is at least equal to or greater than that of the dyes, in order to prevent their simultaneous separation from the dye solution.
  • the task was to find a process that is easy to carry out and does not have any special requirements for the molecular weight that the cations that can be used for the exchange pose.
  • the present invention thus relates to a process for converting sparingly soluble salts of dyes and optical brighteners into more soluble salts by means of cation exchange, without intermediate isolation of the free color acid, the cation exchange being carried out using Donnan dialysis.
  • an exchanger cell is advantageously used, which is divided into two chambers by means of a semipermeable membrane, each of which has an inlet opening that is tangential to the membrane surface and a central outlet opening.
  • Both the dye or brightener solution or suspension as well as the dialysis solution are pumped from the storage cell through the exchanger cell and back into the exchange cell by means of a pump during the exchange process, which closes the circuit.
  • the forced circulation through the exchanger cell should preferably be carried out in such a way that the solutions or suspensions flow past the membrane in the most turbulent flow possible.
  • the energy introduced by the pumps into the closed system which can be measured as a temperature increase, can, if necessary, be dissipated using heat exchangers.
  • the Donnan dialysis is expediently carried out at a temperature of 20 to 25 ° C.
  • FIG 1 shows schematically the apparatus with which the inventive method is carried out: @ exchanger cell, (9 membrane, (D storage container with dye or brightener solution or suspension, @ storage container with dialysis solution, (9 heat exchangers and @ pumps.
  • Donnan dialysis is a membrane process that is carried out without applying pressure.
  • the membranes used have the property of being permeable both to the cation of the dye or brightener salt and to the cation of the dialysis solution, but the anion of the dialysis solution is scarcely permeable and the dye or brightener anion does not let through.
  • the membranes are cation exchange membranes whose polymer structure is modified by polyfunctional compounds containing anionic groups and whose pores have a diameter of 0.1 to 50 ⁇ m.
  • Polysulfone membranes are preferably used.
  • the polymer backbone of the membrane consists of natural, semi-synthetic or synthetic materials which contain, for example, hydroxyl, amino and / or amidoxime groups as reactive groups. Such materials can be reacted with suitable reagents which contain anionic groups on the one hand and at least one group which is reactive to form a chemical (covalent) bond on the other hand.
  • colored compounds such as reactive dyes containing sulfo groups
  • reactive reagents which contain one or more anionic groups.
  • the sulfo group the sulfato group and the carboxyl radical are also to be mentioned as anionic groups.
  • membranes whose backbone made of an inert polymer, such as. B. polyester or polyethylene, which has been coated with an exchange resin.
  • an exchange resin In the manufacture of such membranes, either a finished exchange resin already containing anionic groups is applied to the polymeric support, or the exchange resin is first polymerized on the support and then modified by the customary methods, for example by sulfonation.
  • cationic groups are e.g. B. the ammonium, phosphonium or sulfonium group.
  • Donnan dialysis can be used, for example, to exchange the cations of the following anionic dyes, especially those containing sulfo groups: nitro, aminoketone, ketone imine, methine, nitrodiphenylamine, quinoline, aminonaphthoquinone or coumarin dyes, in particular anthraquinone and azo dyes, such as monoazo - and disazo dyes or 1: 1 and 1: 2 metal complex dyes, and stilbenazo (xy) dyes. Dyes of the classes mentioned which also contain one or more fiber-reactive radicals are also suitable.
  • the dyes are usually in the sodium salt form or also as the potassium or ammonium salt. If the dye is used as the raw dye, it is advisable to desalt it before dialysis is carried out. The easiest way to do this is with the aid of a membrane separation process, such as. B. hyperfiltration.
  • aqueous solutions of lithium salts e.g. B. lithium halides, especially lithium chloride in question.
  • lithium salts e.g. B. lithium halides, especially lithium chloride in question.
  • ammonium salt solutions or solutions of alkanolammonium salts are suitable.
  • Stilbenzo (xy) dyes for example, have been found to be significantly more water-soluble in the alkanolammonium salt form, that is to say as the di- or triethanolammonium salt, than in the sodium salt form.
  • the solubility of the dyes or optical brighteners, for. T. increase considerably.
  • the water solubility of the sodium salts of azo dyes containing sulfo groups is doubled or tripled when they are converted into the corresponding lithium salts.
  • the concentration of the dye or brightener solution or suspension subjected to the ion exchange is advantageously 10 to 500 g / l. preferably 10 to 300 g / l.
  • the dialysis solution is generally used in a concentration of 0.5 to 3 molar, preferably approximately 1 molar.
  • the dialysis solution is exchanged for a fresh solution after every 24 hours of operation.
  • the dye or brightener solution obtained after carrying out the Donnan dialysis can be concentrated by hyperfiltration and, if appropriate after addition of additives, such as binders, dedusting agents, dispersants and / or coupé agents, can be converted into a solid dye preparation by drying. Thanks to the increased dye concentration, less energy is required to dry. Usual drying methods, in particular spray drying, are used.
  • the concentrated dye or brightener solution can also be processed directly into a storage-stable liquid formulation.
  • the additives customary for liquid formulations such as textile auxiliaries, foam-suppressing agents.
  • Antifreezes, humectants, dispersants and / or antimicrobials the dye or brightener solution only by dilution and / or with the help of coupé agents to a predetermined final dye content.
  • the dye or brightener preparations are used for the production of dyeing / brightening baths, padding liquors or printing pastes, which are primarily for dyeing / brightening or printing textile mate materials made of natural or synthetic fibers and suitable for dyeing paper.
  • the dye of the formula is used as a 22% by weight aqueous solution. After 72 hours of dialysis, approximately 87% of the sodium ions are replaced by lithium ions. This increases the solubility of the dye from 180 g / l to 350 g / l.
  • the dye solution is subjected to Donnan dialysis as an approx. 10% by weight solution (colloidal solution). After 96 hours of operation, 87% of the sodium ions are replaced by lithium ions. The maximum solubility of the dye in water is now 160 g / l. In the sodium salt form, the dye is only up to 80 g / l soluble. During the dialysis, the dye solution is concentrated to a final volume of 400 ml.
  • the water solubility of stilbenazo (xy) dyes in the sodium salt form is very low and is in the range of 1 g / 100 ml.
  • the dye mixture is almost completely in the lithium salt form, the solubility is now approx. 13 g / 100 ml.
  • the final volume of the dye solution is 390 ml.
  • the reactive dyes of the formulas given below are subjected to Donnan dialysis (500 ml each of a 20 to 25% by weight dye solution or suspension) and thus converted from the sodium salt form into the corresponding lithium salt, with an exchange rate between 92 and 97 %.
  • the data on the ion exchange are summarized in a table following the formulas.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Coloring (AREA)
  • Detergent Compositions (AREA)
  • Luminescent Compositions (AREA)

Claims (8)

1. Procédé pour la transformation de sels difficilement solubles de colorants anioniques et azurants optiques anioniques en sels plus facilement solubles, au moyen d'un échange de cations, sans isolement intermédiaire de la forme acide libre des colorants, caractérisé par le fait que l'on effectue l'échange de cations en utilisant la dialyse de Donnan.
2. Procédé selon la revendication 1, caractérisé par le fait que l'on utilise en tant que sels difficilement solubles, les sels de sodium, potassium ou ammonium des colorants ou respectivement azurants optiques.
3. Procédé selon la revendication 1, caractérisé par le fait que l'on effectue la dialyse de Donnan dans une cellule d'échanges dans laquelle la solution ou suspension de colorant ou, respectivement, d'azurant optique, et la solution de dialyse, sont séparées l'une de l'autre par une membrane semiperméable, et on fait passer à la surface de la membrane les deux solutions ou la suspension et la solution.
4. Procédé selon la revendication 3, caractérisé par le fait que l'on utilise en tant que membrane semiperméable une membrane échangeuse de cations dont le squelette polymère est modifié par des composés polyfonctionnels contenant des groupes ioniques, et dont les pores présentent un diamètre de 0,1 à 50 (J.m.
5. Procédé selon la revendication 3, caractérisé par le fait que l'on utilise en tant que membrane une membrane polysulfonée.
6. Procédé selon la revendication 1, caractérisé par le fait que l'on utilise en tant que solution de dialyse, une solution d'un sel de lithium, en particulier une solution de chlorure de lithium.
7. Procédé selon la revendication 3, caractérisé par le fait que la concentration de la solution ou suspension de colorant ou. respectivement, d'azurant optique, est de 10 à 500 g/litre, et la solution de dialyse est 0.5 à 3 M.
8. Procédé selon la revendication 1, caractérisé par le fait qu'après la dialyse de Donnan. on concentre la solution de colorant ou d'azurant optique par hyperfiltration.
EP83810251A 1983-05-04 1983-06-09 Procédé de transformation de sels difficilement solubles de colorants ou d'agents de blanchiment optiques anioniques en sels plus facilement solubles, par échange de cations Expired EP0126830B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH2425/83A CH657144A5 (de) 1983-05-04 1983-05-04 Verfahren zur umwandlung schwerloeslicher salze anionischer farbstoffe und optischer aufheller in leichter loesliche salze mittels kationenaustausch.
CH2425/83 1983-05-04

Publications (2)

Publication Number Publication Date
EP0126830A1 EP0126830A1 (fr) 1984-12-05
EP0126830B1 true EP0126830B1 (fr) 1987-07-29

Family

ID=4233505

Family Applications (1)

Application Number Title Priority Date Filing Date
EP83810251A Expired EP0126830B1 (fr) 1983-05-04 1983-06-09 Procédé de transformation de sels difficilement solubles de colorants ou d'agents de blanchiment optiques anioniques en sels plus facilement solubles, par échange de cations

Country Status (5)

Country Link
US (1) US4560480A (fr)
EP (1) EP0126830B1 (fr)
JP (1) JPS59204661A (fr)
CH (1) CH657144A5 (fr)
DE (1) DE3372795D1 (fr)

Families Citing this family (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH660493A5 (de) * 1984-12-07 1987-04-30 Ciba Geigy Ag Verfahren zur herstellung konzentrierter salzarmer waessriger loesungen von aminotriazinyl-reaktivfarbstoffen.
DE3514348A1 (de) * 1985-04-20 1986-10-23 Basf Ag, 6700 Ludwigshafen Verfahren zur gewinnung von waessrigen loesungen organischer saeuren oder basen aus waessrigen loesungen ihrer salze
DE3521129A1 (de) * 1985-06-13 1986-12-18 Bayer Ag, 5090 Leverkusen Verfahren zur herstellung konzentrierter loesungen von anionischen farbstoffen und farbstoffadditiven
JP2506327B2 (ja) * 1985-09-17 1996-06-12 三菱化学株式会社 スルホン酸リチウム基又はスルホン酸アンモニウム基を有する染料水溶液の製造方法
CH669389A5 (fr) * 1986-02-07 1989-03-15 Basf Ag
DE3629981A1 (de) * 1986-09-03 1988-03-17 Basf Ag Verfahren zum entfernen von saeure aus kathodischen elektrotauchlackier-baedern
DE3631750A1 (de) * 1986-09-18 1988-03-31 Bayer Ag Farbstoffpraeparationen
CH672995A5 (fr) * 1987-07-27 1990-01-31 Ciba Geigy Ag
DK0437184T3 (da) * 1990-01-09 1994-05-16 Ciba Geigy Ag Fremgangsmåde til trichromifarvning eller -trykning af celluloseholdige textilfibermaterialer
ES2150175T3 (es) * 1996-06-26 2000-11-16 Bayer Ag Procedimiento para la obtencion de preparaciones pobres en sales de productos de condensacion.
TW200722487A (en) * 2005-12-15 2007-06-16 Benq Corp Yellow dyes and ink compositions comprising the same
BR112013013916B1 (pt) 2011-02-25 2020-01-07 Mayekawa Mfg. Co., Ltd. Sistema de resfriamento de cabo supercondutor
US10259961B2 (en) 2016-03-24 2019-04-16 Seiko Epson Corporation Ink jet textile printing ink composition, ink set, and printing method
JP6801305B2 (ja) * 2016-03-24 2020-12-16 セイコーエプソン株式会社 インクジェット捺染用インク組成物、インクセット及び記録方法
JP7283249B2 (ja) * 2019-06-19 2023-05-30 セイコーエプソン株式会社 水系インクジェット捺染インク組成物及び捺染方法

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3905949A (en) * 1965-04-29 1975-09-16 Du Pont Stilbene azo lithium salt dyes
DE2451219C3 (de) * 1974-10-29 1978-06-22 Bayer Ag, 5090 Leverkusen Verfahren zur Herstellung konzentrierter Lösungen von Farbstoffen und Farbstoffzwischenprodukten und Verwendung der Lösungen
DE2805891C2 (de) * 1978-02-13 1988-12-22 Bayer Ag, 5090 Leverkusen Konzentrierte Farbstoff- und Aufhellerlösungen, deren Herstellung und Verwendung
US4306946A (en) * 1980-08-18 1981-12-22 General Electric Company Process for acid recovery from waste water

Also Published As

Publication number Publication date
CH657144A5 (de) 1986-08-15
JPH0429708B2 (fr) 1992-05-19
US4560480A (en) 1985-12-24
JPS59204661A (ja) 1984-11-20
DE3372795D1 (en) 1987-09-03
EP0126830A1 (fr) 1984-12-05

Similar Documents

Publication Publication Date Title
EP0126830B1 (fr) Procédé de transformation de sels difficilement solubles de colorants ou d'agents de blanchiment optiques anioniques en sels plus facilement solubles, par échange de cations
EP0197006B1 (fr) Procédé de fabrication de préparations de colorants organiques solubles dans l'eau
EP0287515B1 (fr) Procédé de fabrication de solutions concentrées, aqueuses de colorants organiques solubles dans l'eau
DE2805891C2 (de) Konzentrierte Farbstoff- und Aufhellerlösungen, deren Herstellung und Verwendung
EP0210378B2 (fr) Procédé de fabrication de solutions concentrées de colorants et additifs pour colorants anioniques
EP0169811B1 (fr) Procédé de fabrication de préparations aqueuses à position stable de colorants anioniques
DE3231299A1 (de) Verfahren zur herstellung konzentrierter waesseriger zubereitungen von synthetischen anionischen dispergatoren und deren verwendung
EP0235081A1 (fr) Procédé d'épuration des eaux d'égout contenant des colorants
EP0288434B1 (fr) Procédé de fabrication de préparations de colorants concentrées aqueuses
EP0029960A1 (fr) Solutions concentrées aqueuses de colorants réactifs, exemptes de solvants, et procédé pour leur préparation
EP0302015A2 (fr) Procédé de post-traitement continu d'une suspension aqueuse d'un colorant brut
EP0097125B1 (fr) Procédé d'échange de sels inorganiques peu solubles de colorants ou d'azurants optiques cationiques en sels d'acides organiques facilement solubles
EP0059782B1 (fr) Procédé de fabrication de préparations tinctoriales aqueuses concentrées de colorants anioniques pour le papier ou la laine
EP0024667B1 (fr) Procédé de fabrication de préparations de colorants fluides et leur utilisation
CH626118A5 (en) Process for preparing aqueous dispersions of azo dyes
DE3301870C2 (de) Verfahren zur Herstellung von konzentrierten flüssigen Färbepräparaten
EP0278320B1 (fr) Procédé de fabrication d'une solution concentrée, aqueuse d'un colorant réactif
EP0049802B1 (fr) Matière colorante pour cuir et sa préparation
DE3942467A1 (de) Verfahren zur herstellung lagerstabiler farbstoffloesungen
CH648584A5 (en) Process for preparing concentrated aqueous formulations of anionic dyes
CH617911A5 (en) Process for removing water-soluble ionic compounds from aqueous solutions by ultrafiltration
DE1469606C (de) Wasserdispergierbare Zubereitungen wasserunlöslicher Farbstoffe
DE3410620A1 (de) Verfahren zur verhinderung des gelierens von konzentrierten waessrigen photoaktivatorloesungen
CH650012A5 (en) Process for preparing stable, aqueous dye solutions of anionic dyes
DE19927398A1 (de) Verfahren zur Herstellung von Farbstoffen und/oder Aufhellerzubereitungen

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19830611

AK Designated contracting states

Designated state(s): CH DE FR GB LI

17Q First examination report despatched

Effective date: 19860520

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): CH DE FR GB LI

ET Fr: translation filed
REF Corresponds to:

Ref document number: 3372795

Country of ref document: DE

Date of ref document: 19870903

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Effective date: 19880630

Ref country code: CH

Effective date: 19880630

26N No opposition filed
REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 19920415

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 19920430

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 19920504

Year of fee payment: 10

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Effective date: 19930609

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 19930609

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Effective date: 19940228

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Effective date: 19940301

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST